CN108607519A - A kind of sludge passivator and its application - Google Patents
A kind of sludge passivator and its application Download PDFInfo
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- CN108607519A CN108607519A CN201810547200.7A CN201810547200A CN108607519A CN 108607519 A CN108607519 A CN 108607519A CN 201810547200 A CN201810547200 A CN 201810547200A CN 108607519 A CN108607519 A CN 108607519A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4837—Lignin
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention relates to a kind of sludge passivator and its application, it can effectively solve the problems, such as that heavy metal deactivator application range limitation, passivation effect is poor, preparation method is complicated, recycling difficulty is big, the processing load of heavy metal and removal efficiency are low, technical solution is：A kind of sludge passivator, by weight percent meter：Modified lignin resin mixture 85 94%, quick lime 1 3%, sodium alginate 5 12% are made；First by lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：2：3 ratio mixing, is made modified lignin resin mixture；Quick lime is mixed with sodium alginate again, modified lignin resin mixture is added, embedding bead is made, up to sludge passivator, preparation method of the present invention is simple, novel and unique, energy conservation and environmental protection, have a wide range of application, good passivation effect, convenient for recycling, the processing load of heavy metal and removal efficiency it is high, reliable and stable, economic and social benefit is notable.
Description
Technical field
The present invention relates to field of environment protection, especially a kind of sludge passivator and its application.
Background technology
With the raising of China's Living consumption and the development of urban economy, the construction of urban wastewater treatment equipment is continuous
Reinforce.After large-scale treated sewage, heavy metals in city sewage sludge is processed into the main problem utilized again for sludge.
Lignin is as a kind of cheap and be easy to the paper making waste utilized, itself has certain adsorption capacity, it can be used
In heavy metal ion, the removal of dyestuff and organic pollution.Contain a large amount of oxygen-containing functional groups in lignin molecule, it can be directly as
With heavy metal in waste water ion exchange or chelatropic reaction occur for adsorbent.Lignin itself is the waste of paper pulp papermaking industry, directly
Run in put and not only pollutes environment but also waste of resource.The research and development of economic, efficient lignin-base adsorbent, are both to making
The comprehensive utilization of Liginon Resource in paper black liquor, while again a kind of new technology is provided for the improvement of heavy metal wastewater thereby.In addition, by
It is nontoxic in lignin, it is easily degraded by microorganisms, therefore lignin-base flocculant is a kind of heavy metal absorbent of environmental protection again, it can
Solve the caused secondary pollution in the process of common treating sewage by sewage treating agent.The above advantage based on lignin, lignin
Base adsorbent will have wide practical use during heavy metal containing wastewater treatment.Lignin is a kind of three-dimensional in plant cell
There is the netted aromatic polymer of macromolecule aromatic character, the functional groups such as hydroxyl, carboxyl contained in molecule to make its own
It can use directly as adsorbent, but be limited by itself undefined structure.Variety classes industrial lignin to metal from
The absorption property comparison in difference of son is apparent, and this is mainly due to different separation methods to cause caused by chemistry of lignin's structure change.
Its absorption property can be promoted significantly industrial lignin after being chemically modified.
Natural polymer sodium alginate in nature has many advantages, such as biocompatibility, biodegradability, is answered extensively
For fields such as wastewater treatment and medical treatment.It is dissolved in alkaline solution, makes solution that there is viscosity.Sodium alginate powder is met water and is got wet, micro-
The aquation of grain makes its surface have viscosity.Lignin/sodium alginate blended cross linking microballoon can fix lignin, and increase connects
Contacting surface is accumulated, and effective absorption and the heavy metal ion in recycling sludge and rare earth ion, is a kind of change meeting Green Chemistry
Chemical product.
The result shows that：PH and ionic strength have a significant impact heavy metal ion adsorbed process.Lignin is in acid solution
Be adsorbed with small part and can desorb, but such case is not present in aqueous slkali.Quick lime in the sludge passivator
The pH value of sludge can be improved, the adsorption capacity and performance of lignin adsorbent are improved, effective heavy metal of ionic state is converted
For the sediment of the invalid state such as hydroxide.Compared with traditional adsorbent, microballoon provides the surface area of bigger, has more preferable
Diffusion, dispersion and mass transfer behavior, be conducive to the mud-water separation of precipitation process, immobilization can keep the high concentration and height of adsorbent
Activity helps to improve the processing load and removal efficiency of heavy metal, the presence due to particular functional group and flourishing porous knot
Structure, the microballoon obtained have potential application as specific adsorbent.Therefore, using above-mentioned substance to sludge passivator
It is imperative to reform and innovate.
Invention content
For the above situation, to solve the defect of the prior art, it is an object of the invention to provide a kind of sludge passivator
And its application, can effectively solve heavy metal deactivator application range limitation, passivation effect is poor, preparation method is complicated, recycling
The problem that difficulty is big, heavy metal processing load and removal efficiency are low.
The technical solution that the present invention solves is a kind of sludge passivator, by weight percent meter：Modified lignin resin mixes
Object 85-94%, quick lime 1-3%, sodium alginate 5-12% are made；
Specifically preparation method is：
（1）Prepare modified lignin resin mixture：By lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：
2：3 ratio mixing；
The lignin is：0.1-0.5mg/L flocculation aids are added in alkaline papermaking black liquor, the flocculation aid is polyacrylamide
The mixture of amine, flyash or kaolinic one or two kinds of mixed in equal amounts, the sulfuric acid solution for being 13-17% with mass concentration
As acid out agent, adjusting pH value is 2-3, controlled at 60-70 DEG C, is filtered after black liquor flocculation and delamination, obtains filter cake, filter cake is dried
It is dry, it grinds, obtains lignin；
The lignin sulfonic acid is：Using paper mill spent pulping liquor as raw material, the milk of lime of waste liquid bulking value 10% is added, in 92-
28-32min is heated at 97 DEG C, standing sedimentation obtains sediment, and sediment filters out to obtain supernatant, supernatant volume is added after washing
The sulfuric acid of 45-50%, filtering remove calcium sulfate, then Na are added into filtrate2CO3, until there is no precipitation to generate, 85-95 DEG C
Lower reaction 1.5-2.5 h, make calcium lignosulfonate change into sodium sulfonate, are filtered after standing, and filtrate concentration, crystallisation by cooling obtains lignin
Sulfonic acid；The bulking value refers to solid based on g, and liquid is based on ml；
Glutamic acid-the lignin is：1.5-2.5 g lignin is dissolved in 15-25mL lye, 3-4mL matter is added after stirring
The formalin of a concentration of 35-40% is measured, the paddy ammonia that 18-22mL mass fractions are 8-12% is added dropwise in stirring 8-12 min, 30min
Acid sodium solution adjusts pH to 9-10, is placed in 50-70 DEG C of water-bath 3.5-4.5 h, 8-12ml sulfuric acid, 4500- is added in product
5500 r/min are centrifuged 8-12 minute, and precipitation uses sulfuric acid scrubbing 3-5 times of mass concentration 18-22%, then is fully washed to pH with water
For 7.3-7.7, is ground after 45-55 DEG C of drying, obtain glutamic acid-lignin；
（2）Quick lime is mixed with sodium alginate：
It is added the water of its bulking value 1-2.2% into quick lime, sodium alginate is added the water of its bulking value 4-15%, then by two
Person stirs evenly, and until solution is sticky porous, obtains viscous solution；
（3）By step（1）Step is added in the modified lignin resin mixture of gained（2）In the viscous solution of preparation, 8- is stirred
12min,
Uniformly, mixed liquor is obtained, wherein modified lignin resin mixture quality score is 80-92%.
（4）By step（3）Embedding bead is made in solution：
20-25ml steps are drawn with asepsis injector（3）The mixed liquor of preparation slowly instills molar concentration 0.05mol/l's
CaCl2In solution, at 4 DEG C overnight, is washed twice with sterile saline after taking-up, the fixation of a diameter of 1.5-2.5mm is made
Change glue bead, modified lignin resin is embedded in seaweed Calciofon gel to get sludge passivator.
Preparation method of the present invention is simple, novel and unique, energy conservation and environmental protection, has a wide range of application, good passivation effect, is convenient for recycling profit
High with, the processing load of heavy metal and removal efficiency, reliable and stable, economic and social benefit is notable.
Specific implementation mode
It elaborates with reference to embodiments to the specific implementation mode of the present invention.
The present invention in specific implementation, is realized by following embodiment.
Embodiment 1
The present invention in specific implementation, is realized by following steps：
A kind of sludge passivator of the present invention, by weight percent meter：Modified lignin resin mixture 85%, quick lime 3%, alginic acid
Sodium 12% is made；
Specifically preparation method is：
（1）Prepare modified lignin resin mixture：By lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：
2：3 ratio mixing；
The lignin is：0.1mg/L flocculation aid polyacrylamides are added in alkaline papermaking black liquor, are 13% with mass concentration
Sulfuric acid solution as acid out agent, it is 2 to adjust pH values, controlled at 60 DEG C, is filtered after black liquor flocculation and delamination, obtains filter cake, will
Filter cake is dried, and is ground, is obtained lignin；
The lignin sulfonic acid is：Using paper mill spent pulping liquor as raw material, the milk of lime of waste liquid bulking value 10% is added, 92
32 min are heated at DEG C, standing sedimentation obtains sediment, and sediment filters out to obtain supernatant, and supernatant volume 45% is added after washing
Sulfuric acid, filtering remove calcium sulfate, then Na are added into filtrate2CO3, until there is no precipitation to generate, react 2.5 at 85 DEG C
H makes calcium lignosulfonate change into sodium sulfonate, is filtered after standing, and filtrate concentration, crystallisation by cooling obtains lignin sulfonic acid；The weight
Volume refers to solid based on g, and liquid is based on ml；
Glutamic acid-the lignin is：1.5g lignin is dissolved in 15mL lye, 3mL mass concentrations are added after stirring is
35% formalin stirs 8min, the monosodium glutamate solution that 18mL mass fractions are 8% is added dropwise in 30min, adjusts pH to 9, be placed in
8ml sulfuric acid is added in product by 50 DEG C of 4.5 h of water-bath, and 4500r/min is centrifuged 12 minutes, the sulphur of precipitation mass concentration 18%
Acid elution 3 times, then fully washed to pH with water to be ground after 7.3,45 DEG C of dryings, obtain glutamic acid-lignin；
（2）Quick lime is mixed with sodium alginate
The water of its bulking value 1% is added into quick lime, the water of its bulking value 4% is added in sodium alginate, then the two is stirred
Uniformly, until solution is sticky porous, viscous solution is obtained；
（3）By step（1）Step is added in the modified lignin resin mixture of gained（2）In the viscous solution of preparation, 8min is stirred,
It is even, mixed liquor is obtained, wherein modified lignin resin mixture quality score is 80%；
（4）By step（3）Embedding bead is made in solution：
20ml steps are drawn with asepsis injector（3）The mixed liquor of preparation slowly instills the CaCl of molar concentration 0.05mol/l2
In solution, at 4 DEG C overnight, is washed twice with sterile saline after taking-up, the immobilization glue bead of a diameter of 1.5mm is made, changes
Property lignin is embedded in seaweed Calciofon gel to get sludge passivator.
Embodiment 2
The present invention in specific implementation, is realized by following steps：
A kind of sludge passivator, by weight percent meter：Modified lignin resin mixture 88%, quick lime 2%, sodium alginate 10%
It is made；
Specifically preparation method is：
（1）Prepare modified lignin resin mixture：By lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：
2：3 ratio mixing；
The lignin is：0.3mg/L flocculation aid flyash is added in alkaline papermaking black liquor, the sulphur for being 15% with mass concentration
For acid solution as acid out agent, it is 2.5 to adjust pH values, controlled at 65 DEG C, is filtered after black liquor flocculation and delamination, obtains filter cake, will filter
Cake is dried, and is ground, is obtained lignin；
The lignin sulfonic acid is：Using paper mill spent pulping liquor as raw material, the milk of lime of waste liquid bulking value 10% is added, 95
30 min are heated at DEG C, standing sedimentation obtains sediment, and sediment filters out to obtain supernatant, and supernatant volume 47% is added after washing
Sulfuric acid, filtering remove calcium sulfate, then Na are added into filtrate2CO3, until there is no precipitation to generate, 2h is reacted at 90 DEG C, is made
Calcium lignosulfonate changes into sodium sulfonate, is filtered after standing, and filtrate concentration, crystallisation by cooling obtains lignin sulfonic acid；The bulking value
Refer to solid based on g, liquid is based on ml；
Glutamic acid-the lignin is：2.0g lignin is dissolved in 20mL lye, 3.5mL mass concentrations are added after stirring is
38% formalin stirs 10min, the monosodium glutamate solution that 20mL mass fractions are 10% is added dropwise in 30min, adjusts pH to 9.5,
60 DEG C of water-bath 4.0h are placed in, 10ml sulfuric acid is added in product, 5000 r/min are centrifuged 10 minutes, precipitation mass concentration
20% sulfuric acid scrubbing 4 times, then fully washed to pH with water to be ground after 7.5,50 DEG C of dryings, obtain glutamic acid-lignin；
（2）Quick lime is mixed with sodium alginate
The water of its bulking value 1.8% is added into quick lime, the water of its bulking value 10% is added in sodium alginate, then the two is stirred
It mixes uniformly, until solution is sticky porous, obtains viscous solution；
（3）By step（1）Step is added in the modified lignin resin mixture of gained（2）In the viscous solution of preparation, 10min is stirred,
Uniformly, mixed liquor is obtained, wherein modified lignin resin mixture quality score is 86%；
（4）By step（3）Embedding bead is made in solution：
22ml steps are drawn with asepsis injector（3）The mixed liquor of preparation slowly instills the CaCl of molar concentration 0.05mol/l2
In solution, at 4 DEG C overnight, is washed twice with sterile saline after taking-up, the immobilization glue bead of a diameter of 2.0mm is made, changes
Property lignin is embedded in seaweed Calciofon gel to get sludge passivator.
Embodiment 3
The present invention in specific implementation, is realized by following steps：
A kind of sludge passivator, by weight percent meter：Modified lignin resin mixture 94%, quick lime 1%, sodium alginate 5% are made
At；
Specifically preparation method is：
（1）Prepare modified lignin resin mixture：By lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：
2：3 ratio mixing；
The lignin is：0.5mg/L flocculation aids, that is, flyash and kaolin mixed in equal amounts are added in alkaline papermaking black liquor
Mixture uses the sulfuric acid solution that mass concentration is 17% as acid out agent, and it is 3 to adjust pH values, and controlled at 70 DEG C, black liquor is wadded a quilt with cotton
It is filtered after solidifying layering, obtains filter cake, filter cake is dried, ground, obtain lignin；
The lignin sulfonic acid is：Using paper mill spent pulping liquor as raw material, the milk of lime of waste liquid bulking value 10% is added, 97
28 min are heated at DEG C, standing sedimentation obtains sediment, and sediment filters out to obtain supernatant, and supernatant volume 50% is added after washing
Sulfuric acid, filtering remove calcium sulfate, then Na are added into filtrate2CO3, until not having precipitation to generate, 1.5h is reacted at 95 DEG C,
So that calcium lignosulfonate is changed into sodium sulfonate, filtered after standing, filtrate concentration, crystallisation by cooling obtains lignin sulfonic acid；The weighing body
Product refers to solid based on g, and liquid is based on ml；
Glutamic acid-the lignin is：2.5 g lignin are dissolved in 25mL lye, 4mL mass concentrations are added after stirring is
40% formalin stirs 12 min, the monosodium glutamate solution that 22mL mass fractions are 12% is added dropwise in 30min, adjusts pH to 10,
70 DEG C of 3.5 h of water-bath are placed in, 12ml sulfuric acid is added in product, 5500 r/min are centrifuged 8 minutes, precipitation mass concentration
22% sulfuric acid scrubbing 5 times, then fully washed to pH with water to be ground after 7.7,55 DEG C of dryings, obtain glutamic acid-lignin；
（2）Quick lime is mixed with sodium alginate
The water of its bulking value 2.2% is added into quick lime, the water of its bulking value 15% is added in sodium alginate, then the two is stirred
It mixes uniformly, until solution is sticky porous, obtains viscous solution；
（3）By step（1）Step is added in the modified lignin resin mixture of gained（2）In the viscous solution of preparation, 12min is stirred,
Uniformly, mixed liquor is obtained, wherein modified lignin resin mixture quality score is 92%；
（4）By step（3）Embedding bead is made in solution：
20-25ml steps are drawn with asepsis injector（3）The mixed liquor of preparation slowly instills molar concentration 0.05mol/l's
CaCl2In solution, at 4 DEG C overnight, is washed twice with sterile saline after taking-up, the immobilization glue of a diameter of 2.5mm is made
Pearl, modified lignin resin are embedded in seaweed Calciofon gel to get sludge passivator.
The processing of product in the present embodiment effective for paper mill sludge.
The present invention achieves consistent effect through repeatedly testing repeatedly, and correlation test data is as follows：
Experiment one
Heavy metal deactivator made from side of the present invention and sludge are uniformly mixed into experimental group according to 5 kinds of different proportion progress, it is blunt
Agent is with sludge quality than being respectively 1：20,1：25,1：30,1：35,1：40, to be not added with the sludge of passivator as blank control,
After processing 6 months, the heavy metal concentration in passivator treated sludge and the sludge of blank control, experimental result are detected respectively
It is shown in Table 1.
The influence of 1 passivator of table and municipal sludge different specific weight counterweight metal passivation effect
Experiment two
Heavy metal deactivator made from side of the present invention and sludge are uniformly mixed into experimental group according to 5 kinds of different proportion progress, it is blunt
Agent is with sludge quality than being respectively 1：20,1：25,1：30,1：35,1：40, to be not added with the sludge of passivator as blank control,
Respectively that growing way is identical, identical 6 arabidopsis of height are planted into the basin of different experiments group and blank control group, growth six
After a month, the heavy metal concentration in different experiments group and blank control group arabidopsis is detected respectively, and experimental result is shown in Table 2.
Content of beary metal in arabidopsis after 2 passivator of table processing sludge
As can be seen from Table 1 and Table 2, heavy metal deactivator produced by the present invention all has is passivated Heavy Metals in Sludge well
Effect, and the effect for being grown on the content of beary metal of plant in sludge can be reduced well.It as shown in Table 1, will be of the invention
When obtained heavy metal deactivator is mixed with the uniform different proportion of sludge, the content of remaining heavy metal is different in sludge.Passivation
Agent proportion is bigger, and passivation effect is better.From the experimental results, heavy metal Cu, Cd, Zn etc. are 1：It is all had when 30 proportion preferably
Passivation effect, therefore consider cost, proportion 1：30 is more suitable.In addition, compared with blank control group, passivator and dirt
Mud proportion is 1：When 40, passivator has significantly passivation effect, and other than Pb, the content of other heavy metals is below
GB4284-84《Pollutant catabolic gene standard in agricultural sludge》.When passivator and sludge proportion are 1：When 20, Pb contents are
4.97mg/kg also significantly lower than《Pollutant catabolic gene standard in agricultural sludge》.It therefore can be in conjunction with different heavy metals in sludge
Content selects suitable proportion proportioning.
As can be seen from Table 2, content of beary metal is not yet when passivator is mixed with the uniform different proportion of sludge, in arabidopsis
Together.Several Heavy Metallic Elements accumulation in various degree in plant, wherein more serious with Zn Accumulation of Elements.Heavy metal is not
It is smaller with the lower cumulant difference of processing, and variation tendency fluctuation is smaller.Passivator proportion is bigger, and content of beary metal is got in arabidopsis
It is low.When passivator and sludge proportion are 1：When 20, the content of above 6 heavy metal species is below GB 2762-2012《In food
Pollutant is limited the quantity》.Compared with blank control group, passivator is 1 with sludge proportion：When 40, passivator has significantly passivation effect
Fruit, and other than Pb, the content of other heavy metals is below GB 2762-2012《Pollutants in food is limited the quantity》.Passivator with
Sludge proportion is 1：When 35, the content of above 6 heavy metal species is below GB 2762-2012《Pollutants in food is limited the quantity》.This
Plant is higher to the cumulant of Zn in experiment, China's soil and the universal zinc-deficiency of human body, shows for agricultural to lead to sludge
The mode for crossing food chain feeds the scarce element of human body institute.It these results suggest that, lignin, lignin sulfonic acid, paddy ammonia in passivator
Acid-lignin, quick lime and sodium alginate can cooperate under special ratios, act synergistically, and playing reduces in sludge effectively
The effect of state heavy metal.
The present invention provides a kind of sludge passivator, including lignin mixture, quick lime and sodium alginate, the sludge is blunt
Soda lime in agent can improve the pH value of sludge, the adsorption capacity and performance of lignin adsorbent be improved, by ionic state
Effective heavy metal is converted into the sediment of the invalid state such as hydroxide, and sodium alginate has good chelation to heavy metal,
Lignin all has one to the invalid heavy metal such as effective heavy metal, hydroxide states of matter heavy metal and complex state heavy metal of ionic state
Fixed suction-operated.And the adsorbable removal different type heavy metal of different lignin in lignin mixture, overcome absorption
The limitation of heavy metal type, and mixture is at low cost, is easier to obtain.Wherein sodium lignin sulfonate is production paper pulp
By-product has very strong dispersibility, can be adsorbed on the surface of various solid particles, can be by lignin mixture and seaweed
Sour sodium uniformly mixes.Lignosulfonates are soluble in water, are not easy to remove from waste liquid after adsorbing heavy metal, and system of the present invention
Standby passivator bead is conducive to that treated and is separated by solid-liquid separation.The more acid/bases of glutamic acid-lignin copolymer area load
Property adsorption potential, can preferably adapt to different acid or alkali environments.Complementary association between compatibility, performance three between lignin mixture
Tune acts on, and can be passivated variety classes heavy metal.Lignin, quick lime and sodium alginate in above-mentioned passivator can be in specific proportionings
Lower mutual cooperation, synergistic effect play the role of reducing most type available heavy metal contents in sludge, overcome with
The defect single toward the heavy metal-passivated type of passivator also has and improves sludge pH value, improves sludge function and will not cause two
The advantage of secondary pollution, suitable for the produced sludge heavy-metal Passivation Treatment of industrial wastewater.
Claims (5)
1. a kind of sludge passivator, which is characterized in that by weight percent meter：Modified lignin resin mixture 85-94%, raw stone
Grey 1-3%, sodium alginate 5-12% are made；
Specifically preparation method is：
（1）Prepare modified lignin resin mixture：By lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：
2：3 ratio mixing；
The lignin is：0.1-0.5mg/L flocculation aids are added in alkaline papermaking black liquor, the flocculation aid is polyacrylamide
The mixture of amine, flyash or kaolinic one or two kinds of mixed in equal amounts, the sulfuric acid solution for being 13-17% with mass concentration
As acid out agent, adjusting pH values are 2-3, controlled at 60-70 DEG C, are filtered after black liquor flocculation and delamination, filter cake are obtained, by filter cake
Drying grinds, obtains lignin；
The lignin sulfonic acid is：Using paper mill spent pulping liquor as raw material, the milk of lime of waste liquid bulking value 10% is added, in 92-
28-32 min are heated at 97 DEG C, standing sedimentation obtains sediment, and sediment filters out to obtain supernatant, supernatant volume is added after washing
The sulfuric acid of 45-50%, filtering remove calcium sulfate, then Na are added into filtrate2CO3, until there is no precipitation to generate, 85-95 DEG C
Lower reaction 1.5-2.5 h, make calcium lignosulfonate change into sodium sulfonate, are filtered after standing, and filtrate concentration, crystallisation by cooling obtains lignin
Sulfonic acid；The bulking value refers to solid based on g, and liquid is based on ml；
Glutamic acid-the lignin is：1.5-2.5 g lignin is dissolved in 15-25mL lye, 3-4mL matter is added after stirring
The formalin of a concentration of 35-40% is measured, the paddy ammonia that 18-22mL mass fractions are 8-12% is added dropwise in stirring 8-12 min, 30min
Acid sodium solution adjusts pH to 9-10, is placed in 50-70 DEG C of water-bath 3.5-4.5 h, 8-12ml sulfuric acid, 4500- is added in product
5500 r/min are centrifuged 8-12 minute, and precipitation uses sulfuric acid scrubbing 3-5 times of mass concentration 18-22%, then is fully washed to pH with water
For 7.3-7.7, is ground after 45-55 DEG C of drying, obtain glutamic acid-lignin；
（2）Quick lime is mixed with sodium alginate：
It is added the water of its bulking value 1 ~ 2.2% into quick lime, sodium alginate is added the water of its bulking value 4 ~ 15%, then by two
Person stirs evenly, and until solution is sticky porous, obtains viscous solution；
（3）By step（1）Step is added in the modified lignin resin mixture of gained（2）In the viscous solution of preparation, 8- is stirred
12min,
Uniformly, mixed liquor is obtained, wherein modified lignin resin mixture quality score is 80-92%；
（4）By step（3）Embedding bead is made in solution：
20-25ml steps are drawn with asepsis injector（3）The mixed liquor of preparation slowly instills molar concentration 0.05mol/l's
CaCl2In solution, at 4 DEG C overnight, is washed twice with sterile saline after taking-up, the fixation of a diameter of 1.5-2.5mm is made
Change glue bead, modified lignin resin is embedded in seaweed Calciofon gel to get sludge passivator.
2. sludge passivator according to claim 1, which is characterized in that by weight percent meter：Modified lignin resin is mixed
Object 85%, quick lime 3%, sodium alginate 12% is closed to be made；
Specifically preparation method is：
（1）Prepare modified lignin resin mixture：By lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：
2：3 ratio mixing；
The lignin is：0.1mg/L flocculation aid polyacrylamides are added in alkaline papermaking black liquor, are 13% with mass concentration
Sulfuric acid solution as acid out agent, it is 2 to adjust pH values, controlled at 60 DEG C, is filtered after black liquor flocculation and delamination, obtains filter cake, will
Filter cake is dried, and is ground, is obtained lignin；
The lignin sulfonic acid is：Using paper mill spent pulping liquor as raw material, the milk of lime of waste liquid bulking value 10% is added, 92
32 min are heated at DEG C, standing sedimentation obtains sediment, and sediment filters out to obtain supernatant, and supernatant volume 45% is added after washing
Sulfuric acid, filtering remove calcium sulfate, then Na are added into filtrate2CO3, until there is no precipitation to generate, react 2.5 at 85 DEG C
H makes calcium lignosulfonate change into sodium sulfonate, is filtered after standing, and filtrate concentration, crystallisation by cooling obtains lignin sulfonic acid；The weight
Volume refers to solid based on g, and liquid is based on ml；
Glutamic acid-the lignin is：1.5g lignin is dissolved in 15mL lye, 3mL mass concentrations are added after stirring is
35% formalin stirs 8min, the monosodium glutamate solution that 18mL mass fractions are 8% is added dropwise in 30min, adjusts pH to 9, be placed in
8ml sulfuric acid is added in product by 50 DEG C of 4.5 h of water-bath, and 4500r/min is centrifuged 12 minutes, the sulphur of precipitation mass concentration 18%
Acid elution 3 times, then fully washed to pH with water to be ground after 7.3,45 DEG C of dryings, obtain glutamic acid-lignin；
（2）Quick lime is mixed with sodium alginate
The water of its bulking value 1% is added into quick lime, the water of its bulking value 4% is added in sodium alginate, then the two is stirred
Uniformly, until solution is sticky porous, viscous solution is obtained；
（3）By step（1）Step is added in the modified lignin resin mixture of gained（2）In the viscous solution of preparation, 8min is stirred,
Uniformly, mixed liquor is obtained, wherein modified lignin resin mixture quality score is 80%；
（4）By step（3）Embedding bead is made in solution：
20ml steps are drawn with asepsis injector（3）The mixed liquor of preparation slowly instills the CaCl of molar concentration 0.05mol/l2It is molten
In liquid, at 4 DEG C overnight, is washed twice with sterile saline after taking-up, the immobilization glue bead of a diameter of 1.5mm is made, it is modified
Lignin is embedded in seaweed Calciofon gel to get sludge passivator.
3. sludge passivator according to claim 1, which is characterized in that by weight percent meter：Modified lignin resin is mixed
Object 88%, quick lime 2%, sodium alginate 10% is closed to be made；
Specifically preparation method is：
（1）Prepare modified lignin resin mixture：By lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：
2：3 ratio mixing；
The lignin is：0.3mg/L flocculation aid flyash is added in alkaline papermaking black liquor, the sulphur for being 15% with mass concentration
For acid solution as acid out agent, it is 2.5 to adjust pH values, controlled at 65 DEG C, is filtered after black liquor flocculation and delamination, obtains filter cake, will filter
Cake is dried, and is ground, is obtained lignin；
The lignin sulfonic acid is：Using paper mill spent pulping liquor as raw material, the milk of lime of waste liquid bulking value 10% is added, 95
30 min are heated at DEG C, standing sedimentation obtains sediment, and sediment filters out to obtain supernatant, and supernatant volume 47% is added after washing
Sulfuric acid, filtering remove calcium sulfate, then Na are added into filtrate2CO3, until there is no precipitation to generate, 2h is reacted at 90 DEG C, is made
Calcium lignosulfonate changes into sodium sulfonate, is filtered after standing, and filtrate concentration, crystallisation by cooling obtains lignin sulfonic acid；The bulking value
Refer to solid based on g, liquid is based on ml；
Glutamic acid-the lignin is：2.0g lignin is dissolved in 20mL lye, 3.5mL mass concentrations are added after stirring is
38% formalin stirs 10min, the monosodium glutamate solution that 20mL mass fractions are 10% is added dropwise in 30min, adjusts pH to 9.5,
60 DEG C of water-bath 4.0h are placed in, 10ml sulfuric acid is added in product, 5000 r/min are centrifuged 10 minutes, precipitation mass concentration
20% sulfuric acid scrubbing 4 times, then fully washed to pH with water to be ground after 7.5,50 DEG C of dryings, obtain glutamic acid-lignin；
（2）Quick lime is mixed with sodium alginate
The water of its bulking value 1.8% is added into quick lime, the water of its bulking value 10% is added in sodium alginate, then the two is stirred
It mixes uniformly, until solution is sticky porous, obtains viscous solution；
（3）By step（1）Step is added in the modified lignin resin mixture of gained（2）In the viscous solution of preparation, 10min is stirred,
Uniformly, mixed liquor is obtained, wherein modified lignin resin mixture quality score is 86%；
（4）By step（3）Embedding bead is made in solution：
22ml steps are drawn with asepsis injector（3）The mixed liquor of preparation slowly instills the CaCl of molar concentration 0.05mol/l2It is molten
In liquid, at 4 DEG C overnight, is washed twice with sterile saline after taking-up, the immobilization glue bead of a diameter of 2.0mm is made, it is modified
Lignin is embedded in seaweed Calciofon gel to get sludge passivator.
4. sludge passivator according to claim 1, which is characterized in that by weight percent meter：Modified lignin resin is mixed
Object 94%, quick lime 1%, sodium alginate 5% is closed to be made；
Specifically preparation method is：
（1）Prepare modified lignin resin mixture：By lignin, sodium lignin sulfonate and glutamic acid-lignin according to mass ratio 4：
2：3 ratio mixing；
The lignin is：0.5mg/L flocculation aids, that is, flyash and kaolin mixed in equal amounts are added in alkaline papermaking black liquor
Mixture uses the sulfuric acid solution that mass concentration is 17% as acid out agent, and it is 3 to adjust pH values, and controlled at 70 DEG C, black liquor is wadded a quilt with cotton
It is filtered after solidifying layering, obtains filter cake, filter cake is dried, ground, obtain lignin；
The lignin sulfonic acid is：Using paper mill spent pulping liquor as raw material, the milk of lime of waste liquid bulking value 10% is added, 97
28 min are heated at DEG C, standing sedimentation obtains sediment, and sediment filters out to obtain supernatant, and supernatant volume 50% is added after washing
Sulfuric acid, filtering remove calcium sulfate, then Na are added into filtrate2CO3, until not having precipitation to generate, 1.5h is reacted at 95 DEG C,
So that calcium lignosulfonate is changed into sodium sulfonate, filtered after standing, filtrate concentration, crystallisation by cooling obtains lignin sulfonic acid；The weighing body
Product refers to solid based on g, and liquid is based on ml；
Glutamic acid-the lignin is：2.5 g lignin are dissolved in 25mL lye, 4mL mass concentrations are added after stirring is
40% formalin stirs 12 min, the monosodium glutamate solution that 22mL mass fractions are 12% is added dropwise in 30min, adjusts pH to 10,
70 DEG C of 3.5 h of water-bath are placed in, 12ml sulfuric acid is added in product, 5500 r/min are centrifuged 8 minutes, precipitation mass concentration
22% sulfuric acid scrubbing 5 times, then fully washed to pH with water to be ground after 7.7,55 DEG C of dryings, obtain glutamic acid-lignin；
（2）Quick lime is mixed with sodium alginate
The water of its bulking value 2.2% is added into quick lime, the water of its bulking value 15% is added in sodium alginate, then the two is stirred
It mixes uniformly, until solution is sticky porous, obtains viscous solution；
（3）By step（1）Step is added in the modified lignin resin mixture of gained（2）In the viscous solution of preparation, 12min is stirred,
Uniformly, mixed liquor is obtained, wherein modified lignin resin mixture quality score is 92%；
（4）By step（3）Embedding bead is made in solution：
20-25ml steps are drawn with asepsis injector（3）The mixed liquor of preparation slowly instills molar concentration 0.05mol/l's
CaCl2In solution, at 4 DEG C overnight, is washed twice with sterile saline after taking-up, the immobilization glue of a diameter of 2.5mm is made
Pearl, modified lignin resin are embedded in seaweed Calciofon gel to get sludge passivator.
5. application of -4 any one of them sludge passivator of claims 1 or 2 in sewage disposal.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321132A (en) * | 2020-12-04 | 2021-02-05 | 河南工程学院 | Municipal sludge treatment and utilization method |
| CN112774584A (en) * | 2019-11-08 | 2021-05-11 | 华南农业大学 | Floatable FeS-lignin hydrogel nanocomposite and preparation method and application thereof |
| CN112897686A (en) * | 2021-01-28 | 2021-06-04 | 海南天鸿市政设计股份有限公司 | Immobilized activated sludge and preparation method thereof |
| CN114835916A (en) * | 2022-06-14 | 2022-08-02 | 齐鲁工业大学 | Threonine modified lignin flocculant and preparation method thereof |
| CN115028247A (en) * | 2022-06-14 | 2022-09-09 | 齐鲁工业大学 | Guanidinoacetic acid modified lignin flocculant and preparation method thereof |
| CN115043476A (en) * | 2022-06-24 | 2022-09-13 | 齐鲁工业大学 | Serine modified lignin flocculant and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5352622A (en) * | 1976-10-22 | 1978-05-13 | Meiji Seika Kaisha Ltd | Composition for preparation of bordeaux mixture |
| CN103548094A (en) * | 2011-04-28 | 2014-01-29 | 学校法人慈惠大学 | Magnetic composite particles for decontamination and method for producing same, and system for decontaminating radioactive materials and method for decontaminating radioactive materials |
| CN103787558A (en) * | 2012-11-01 | 2014-05-14 | 深圳市海川实业股份有限公司 | Heavy metal stabilizer used for sludge treatment, and method for treating sludge by adopting it |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
| CN106582550A (en) * | 2016-11-10 | 2017-04-26 | 广西大学 | Lignin xanthate bentonite composite ball and preparation method thereof |
-
2018
- 2018-05-31 CN CN201810547200.7A patent/CN108607519B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5352622A (en) * | 1976-10-22 | 1978-05-13 | Meiji Seika Kaisha Ltd | Composition for preparation of bordeaux mixture |
| CN103548094A (en) * | 2011-04-28 | 2014-01-29 | 学校法人慈惠大学 | Magnetic composite particles for decontamination and method for producing same, and system for decontaminating radioactive materials and method for decontaminating radioactive materials |
| CN103787558A (en) * | 2012-11-01 | 2014-05-14 | 深圳市海川实业股份有限公司 | Heavy metal stabilizer used for sludge treatment, and method for treating sludge by adopting it |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
| CN106582550A (en) * | 2016-11-10 | 2017-04-26 | 广西大学 | Lignin xanthate bentonite composite ball and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FANG ZHOU,ET AL: "High performance of 3D porous graphene/lignin/sodium alginate composite for adsorption of Cd(II) and Pb(II)", 《ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH VOLUME》 * |
| 马英梅等: "谷氨酸-木质素吸附剂的制备及对Pb2+的吸附性能", 《东北林业大学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112774584A (en) * | 2019-11-08 | 2021-05-11 | 华南农业大学 | Floatable FeS-lignin hydrogel nanocomposite and preparation method and application thereof |
| CN112774584B (en) * | 2019-11-08 | 2022-03-22 | 华南农业大学 | Floatable FeS-lignin hydrogel nanocomposite and preparation method and application thereof |
| CN112321132A (en) * | 2020-12-04 | 2021-02-05 | 河南工程学院 | Municipal sludge treatment and utilization method |
| CN112897686A (en) * | 2021-01-28 | 2021-06-04 | 海南天鸿市政设计股份有限公司 | Immobilized activated sludge and preparation method thereof |
| CN114835916A (en) * | 2022-06-14 | 2022-08-02 | 齐鲁工业大学 | Threonine modified lignin flocculant and preparation method thereof |
| CN115028247A (en) * | 2022-06-14 | 2022-09-09 | 齐鲁工业大学 | Guanidinoacetic acid modified lignin flocculant and preparation method thereof |
| CN115028247B (en) * | 2022-06-14 | 2023-12-22 | 齐鲁工业大学 | Guanidinoacetic acid modified lignin flocculant and preparation method thereof |
| CN115043476A (en) * | 2022-06-24 | 2022-09-13 | 齐鲁工业大学 | Serine modified lignin flocculant and preparation method thereof |
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